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Structures, Energetics, and Infrared Spectra of the Cationic Monomethylamine-Water Clusters
Shu-kang Jiang1,2,3,4, Dong Yang2,4, Xiang-tao Kong2, Chong Wang2,4, Xiang-yu Zang2,4, Hui-jun Zheng2,4, Gang Li2, Hua Xie2, Wei-qing Zhang2, Xue-ming Yang1,2,3, Ling Jiang*2
1.Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China;2.State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China;3.School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China;4.University of Chinese Academy of Sciences, Beijing 100049, China
Abstract:
The structures, energetics, and infrared (IR) spectra of the cationic monomethylamine-water clusters, [(CH3NH2)(H2O)n]+ (n=1-5), have been studied using quantum chemical calculations at the MP2/6-311+G(2d,p) level. The results reveal that the formation of proton-transferred CH2NH3+ ion core structure is preferred via the intramolecular proton transfer from the methyl group to the nitrogen atom and the water molecules act as the acceptor for the O????HN hydrogen bonds with the positively charged NH3+ moiety of CH2NH3+, whose motif is retained in the larger clusters. The CH3NH2+ ion core structure is predicted to be less energetically favorable. Vibrational frequencies of CH stretches, hydrogen-bonded and free NH stretches, and hydrogen-bonded OH stretches in the calculated IR spectra of the CH2NH3+ and CH3NH2+ type structures are different from each other, which would afford the sensitive probes for fundamental understanding of hydrogen bonding networks generated from the radiation-induced chemical processes in the [(CH3NH2)(H2O)n]+ complexes.
Key words:  Monomethylamine, Water, Structure, Energetics, Infrared spectroscopy
FundProject:
甲胺水合离子团簇的结构模型及红外光谱研究
蒋述康1,2,3,4, 杨 冬2,4, 孔祥涛2, 王 冲2,4, 臧翔宇2,4, 郑会俊2,4, 李 刚2, 谢 华2, 张未卿2, 杨学明1,2,3, 江 凌*2
1.中国科学院上海高等研究院,上海 201210;2.中国科学院大连化学物理研究所,分子反应动力学国家重点实验室,大连 116023;3.上海科技大学物质科学与技术学院, 上海 201210;4.中国科学院大学,北京 100049
摘要:
本文利用量子化学计算方法,研究了甲胺和水复合离子团簇[(CH3NH2)(H2O)n]+的几何结构、能量和红外光谱,揭示了结构生长模型、氢键作用机制和质子转移机理. 研究结果表明,在[(CH3NH2)(H2O)n]+团簇中,甲胺甲基上的一个氢原子转移到氨基上,形成分子内质子转移的CH2NH3+离子核心结构模型,水分子作为氢键受体,与质子化氨基NH3+形成氢键. CH3NH2+离子核心结构模型没有CH2NH3+离子核心结构模型稳定. 在团簇的红外光谱中,CH振动、自由NH振动、氢键结合的NH振动和OH振动模式在CH3NH2+和CH2NH3+两种离子核心结构模型的理论计算红外光谱中明显不同,因此可用于鉴别甲胺水合离子团簇的结构模型,有助于理解甲胺和水复合团簇的氢键网络结构.
关键词:  甲胺,水,结构,能学,红外光谱
DOI:10.1063/1674-0068/cjcp1905103
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